Diazine derivatives



Patented July 13, 1943 UNITED STATES PATENT OFFICE DIAZINE DERIVATIVES Gaetnno F. DAlello and James W. Underwood,

Pittsiield, Man, as Company, a oorporat ilnors to General Electric ion of New York No Drawing. Application March 26, 1942,

Serial No.

12 Claims. (01. 260-251) The diazine derivatives of this invention may be represented by the following general formula:

In the above formula n represents an integer and is at least 1 and not more than 2 and R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and substituted hydrocarbon radicals, more particularly halo-hydrocarbon radicals.

Illustrative examples of radicals that R in Formula I may represent are: aliphatic (e. g., methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, isobutyl, butenyl, amyl, isoamyl, hexyl, etc.), including cycloaliphatic (e. g., cyclopentyl, cylcopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, etc.); aryl (e. 8., phenyl, diphenyl or xenyl, naphthyl, etc.); aliphatic-substituted aryl (e. g., tolyl, xylyl, ethylphenyl, propylphenyl, isopropylphenyl, allylphenyl, Z-butenylphenyl, tertiary-butylphenyl, etc.) aryl-substituted aliphatic (e. g., benzyl, phenylethyl, phenylisopropyl, cinnamyl. etc); and their homologues, as well as those groups with one or more of their hydrogen atoms substituted by, for example, a halogen, more particularly chlorine, bromine, fluorine or iodine. Specific examples of halogeno-substituted hydrocarbon radicals are chloromethyl, chloroethyl, chlorophenyl, dichloro- 55 phenyl, chlorocyclohexyl, ethyl chlorophenyl, phenyl chloroethyl, bromoethyl, bromopropyl, bromotolyl, iodophenyl, etc. However, there also may be produced in accordance with the present invention compounds such, for instance, as those represented by the general formulas:

and, more particularly,

SCHr-CHS- A; (NHR)| \N/ N \N/ J where n and B. have the same meanings as above given with reference to Formula I.

The new compounds of this invention may be used, for example, a pharmaceuticals, plasticizers, fungicides, insecticides, as an intermediate in the preparation of dyes and other chemical compounds, for instance as an intermediate in producing derivatives thereof such as ureido, hydrazino, carbamyl, amidine, methylol, etc., derivatives. These new compounds are especially valuable in th preparation of synthetic resinous compositions. Thus, they may be condensed with, for example, aldehydes, including polymeric aldehydes, hydroxy aldehydes and aldehyde-addition products, to yield condensation products of particular utility in the plastics and coating arts. Such condensation products are more fully described and are specifically claimed in our copending application Serial No. 436,248, filed concurrently herewith and assigned to the same assignee as the present invention. These new compounds also may be compounded with rubber, both natural and synthetic, to modify the properties of the rubber.

Various methods may be employed to produce the chemical compounds of this invention. We prefer to prepare them by efl'ectlng reaction between a diamino [(-NHR) :l mercapto pyrimidine and a di-halogenated alkyl cyanide (di-halogenated cyano-alkane) in the presence of a hydro-halide acceptor, the reactants being employed in the ratio of two mols of the diamino mercapto pyrimidine per mol of the ell-halogenated alkyl cyanide. V

Illustrative examples of mercapto diamino pyrimidines that may be used, depending upon the particular end-product desired, are:

R-mercapto 4,6-diamino pyrimidine z-mercapto 4-bromotoluido 8-benzylamino pyrimidine z-mercapto 4-phenvlchloroethylamino G-phenethylamino pyrimidine z-mercapto 4-chloroanilino phenyiamino pyrimidine z-mercapto 4-cycloheptylamino e-isopro'pylphenylamino pyrimidine 2-mercapto 4,8-diamino S-methyl pyrimidine 2-mercapto 4,8-di-(methylamino) pyrimidine z-mercapto 4,6-di-(methylamino) 5-methyl pyrimidine z-mercapto i-chloroethylamino G-methvlamino pyrimidine 2-mercapto 4,6-di-(aniiino) pyrimidine z-mercapto 4,6-di-(anilino) 5-butyl pyrimidine Z-mercapto i-xenylamino 5-cyclopentyl B-amylamino pyrimidine 2-mercapto 4-amino B-ethylamino pyrimidine 2-toluido 4-mercapto 5-cyclohexenyl 6-amino pyrimidine (2-toluido i-amino 5-cyclohexenyl B-mercapto pyrimidine) z-mercapto 4,6-di-(propylamino) pyrimidine z-allylamino 4-mercapto S-phenyl G-amino pyrimidine Z-isoamylamino 4-mercapto 6-chloroanilino pyrimidine z-dichloroanilino i-mercapto 5-tolyl B-propylamino pyrimidine 5-methyl 8-ethylz-cycloheptylamino i-mercapto fi-isobutylamino pyrimidine n-mercapto a-allylamino c-butylamino pyrimidine z-mercapto 4-isobutylamino o-cyciopentyiamino pyrimidine 2 -mercapto 4-(3-butenylamino) s-isopropylamino pyrimidine Typical examples of di-halogenated alkyl cyanides (di-halogenated alkyl nitriles) that may Alpha, alpha-dichloro propionitrile Beta, beta-dichloro propionitrile Alpha, beta-dibromo propionitrile Alpha, alpha-diiodo butyronitrile Alpha, beta-dibromo valeronitrile Beta, beta-dichloro butyronitrile Alpha, alpha-diiodo' beta-methyl butyronitrile Alpha, beta-dichloro alpha, beta-dimethyl butyronitril Alpha, beta-dibromo alpha-methyl beta-benzyl capronitrile Alpha, beta-diiodo alpha-cyclohexyl beta-tolyl butyronltrlie Alpha, alpha-dichloro beta, beta-diphenyl valeronitrile Alpha-chloro alpha-iodo acetonitrile Alpha-chloro beta-bromo alpha-naphthyl betaxylyl butyronitril Dichloroacetonitrile Dibromoacetonitrile Diiodoacetonitrile Alpha, beta-dibromo beta-methyl gamma-phenyl valeronitrile Various hydrohalide acceptors may be employed. We prefer to use a hydrohalide acceptor that will react with the mercapto pyrimidine to form a water-soluble salt. Examples of such acceptors are the alkali-metal hydroxides, e. g., sodium hydroxide, potassium hydroxide, etc. Additional examples of hydrohalide acceptors that may be used are other inorganic bases, e. 3., calcium hydroxide, barium hydroxide, ammonium hydroxide, etc.; carbonates of inorganic bases, including the carbonates of alkali metals; organic amines such as tertiary amines, e. 3., trimethyl amine, triethyl amine, tributyl amine. pyridine, dimethyl aniline, quinoline, etc.; quaternary ammonium bases, e. 3., tetramethyl ammonium hydroxide, etc.; and the like.

The reaction between the mercapto diamino pyrimidine and the di-halogenated alkyl nitrile may be carried out in any suitable manner, but preferably is eflected in the presence of a suitable solvent or mixture oi solvents. Although various solvents and solvent mixtures may be employed, we prefer to use water or a mixture of water and alcohol. The reaction may be carried out under a variety of temperature and pressure conditions, for instance at normal, sub-normal or at elevated temperatures and at atmospheric, sub-atmospheric or super-atmospheric pressures.

The above reaction may be represented by the following general equation:

+2 (Alt oi the hydmhalide scepter) be carried into eflect, th following illustrative examples are given. All parts are by weight.

Example 1 This example illustrates the preparation of alpha, beta-bis-(4,6-diamino pyrimidyl-2) cyanoethylene disulfide, the formula for which is NE: NH:

v HC/ \N N/ J-H HaN-( L c-s-cm-cn-s-c -Na,

\N/ N N Parts (approximately) 4,6-diamino 2-mercapto pyrimidine 142 Alpha, beta-dichloropropionitrile 63 Sodium hydroxide 40 Alcohol 50 Water 50 The sodium hydroxide and the 4,6-diamino pyrimidine were dissolved in the mixture of water and alcohol. The alpha, beta-dichloropropionitrile was now added and the reaction was allowed to proceed at room temperature for about 90 hours.

The reaction mass was then heated under reflux at the boiling temperature of the mass for 1 hour. The mass was stirred during the heating period. After cooling to room temperature the product, alpha, beta-bis-(4,6-diamino pyrimidyl-2) cyanoethylene disulfide, which had precipitated from the mass, 'was filtered from the mother liquor and well washed with water. No attempt was made to recover any more product from the mother liquor. A yield of 131 parts of the dried and purified product was obtained.

Example 2 Alpha, beta-bis-(2,6-diamino pyrimidyl-4) cyanoethylene disulfide, which also may be named alpha, beta-bis-(2,4-diamino pyrimidyl-6) cyanoethylene disulfide, is prepared in essentially the same manner as described under Example 1 with the exception that 142 parts of 2,6-diamino -mercapto pyrimidine is used intead of 142 parts of 4,6-diamino 2-mercapto pyrimidine.

Example 3 A bis-(diamino pyrimidyl) cyanomethylene disulfide, specifically bis-(4,6-diamino pyrimidyl- 2) cyanomethylene disulfide, is produced in essentially the same manner as described under Example 1 with the exception that, instead of alpha, beta-dichloropropionitrile, an equivalent amount of dichloroacetonitrile is used.

Example 4 pyrimidyl-2) cy- Alpha, alpha-bis-(4,6-diamino pyrimidyl-z) cyanoethylidene disulfide Alpha, alpha-bis-(zfi-diamino pyrimidy1-4) cyanoethylidene disulfide- Beta-phenyl alpha,- alpha-bls-(l-pentylamino 5-methyl G-ethylamino pyrimidyl-2) cyanoethylidene disulfide Beta, beta-bis-(4,6-diamino pyrimidyl-Z) cyanopropylidene disulfide Beta, beta-bis-(2,6-diamino propylidene disulfide Alpha, beta-bis- (4,6-diamino pyrimidy1-2) cyanopropylene disulfide Alpha, beta-bis-(2,6-diamino pyrimidy1-4) cyanopropylene disulfide Alpha-methyl beta, beta-bis-(4,6-dianilino 5- phenyl pyrimidyl-2) cyanopropylidene disulfide Alpha, beta-dimethyl alpha, beta-bis-(4-xylidino -benzyl fi-amino pyrimidyl-Z) cyanopropylene disulfide Alpha-butyl alpha, beta-bis-(2-amino 5-cyc1ohexyl 6-naphthylamino pyrimidyll) cyanoethylene disulfide Alpha-cyclopentyl bcta-phenyl alpha, beta-bis- (2-methylamino fi-naphthyl fi-isopropylamino pyrimidyl-4) cyanoethylene disulfide Alpha, beta-di-(chlorophenyl) alpha, beta-bis- (diamino pyrimidyl) cyanoethylene disulfide Beta-benzyl alpha, alpha-bis-(2,6-diamino 5- xylyl pyrimidyl-4) cyanopropylidene disulfide Tolyl bis-(4-anilino 6-methylamino pyrimidyl-2) cyanomethylene disulfide pyrimidyl-4) cyano- Phenyl bis-(diamino pyrimidyl) cyanomethylene' Chlorophenyl bis-(diamino pyrimidyl) cyanomethylene disulfide Bromotolyl bis-(diamino pyrimidyl) methylene disulfide Iodophenyl bis-(diamino pyrimidyl) cyanomethylene disulfide Alpha-benzyl alpha, beta-bis-(4,6-diamino 5- methyl pyrimidyl-2) cyanoethylene disulfide Alpha-butyl alpha, beta-bis'- (2,6-diamino 5- methyl pyrimidyl-4) cyanoethylene disulfide Alpha, beta-dimethyl alpha, beta-bis-(4-cyclopentylamino 5-methyl 6-toluido pyrimidyl-2) cyanoethylene disulfide Alpha, beta-diethyl alpha, beta-bis-(Z-fluoroanilino 5-t0lyl G-toluido pyrimidyl-4) cyanoethylene disulfide Alpha-methyl alpha, beta-bis-(l-benzylamino 5- chlorophenyl 6-amino pyrimidyl-2) cyanoethylene disulfide Alpha, beta-dipropyl alpha, beta-bis-(4-iodoanilino 6-toluido pyrimidyl-2) cyanoethylene disulfide Beta-phenyl alpha, beta-bis-[2,6-di-(methylamino) 5-cyclohexyl pyrimidyl-4] cyanoethylene disulfide Beta-phenyl alpha, beta-bis-(diamino pyrimidyl) cyanoethylene disulfide Beta-tolyl alpha, beta-bis-(diamino pyrimidyl) cyanoethylene disulfide Beta-cyclohexyl alpha, beta-bis-(diamino pyrimidyl) cyanoethylene disulfide Beta-cyclohexenyl alpha, beta-bis-(diamino pyrimidyl) cyanoethylene disulfide Alpha- (2-butenylphenyl) alpha, beta-bis- (diaminopyrimidyl) cyanoethylene disulfide Bis-[di-(naphthylamino) pyrimidyl cyanomethylene disulfide Alpha, beta-bis-[4,6-di-(allylamino) pyrimidyl- 2] cyanoethylene disulfide cyano- Alpha, beta-bis- [4,6-di-(bromoethylamino) pyrimidyl-2] cyanoethylene disulflde Bis-(Z-amino fi-ethylamino pyrimidyl-4) cyanomethylene disulfide Beta-tolyl alpha, alpha-bis-(diamino pyrimidyl) cyanoethylidene disulfide Alpha, beta-bis-(diamino pyrimidyl) cyanobutylene disulfide Alpha, alpha-bis-(diamino pyrimidyl) cyanobutylidene disulfide Beta, beta-bis-(diamino pyrimidyl) cyanobutylidene disulfide Alpha, beta-bis-(diamino pyrimidyl) cyanopentylene disulfide Alpha, beta-bis-(diamino pyrimidyl) cyanohexylene disulfide (BEN);-

Alpha, beta-bis-(diamino pyrimidyl) cyanoheptylene disulfide It will be understood, of course, by those skilled in the art that "diamino pyrimidyl as used broadly in naming some of the above-mentioned compounds includes within its meaning both the bis-(4,6-diamino pyrimidyl-2) and the bis-(2,6- diamino pyrimidyl-4) [bis-(2,4-diamino pyrimidyl-6)] compounds.

In a manner similar to that described above with particular reference to the production of bis-(diamino pyrimidyl) cyanoalkylene disulfides, which also may be named bis-(diamino 1,3- diazinyl) cyanoalkylene disulfides, corresponding derivatives of the 1,2-diazines and of the 1,4- diazines may be prepared.

What we claim as new and desire to secure by Letters Patent of the United States is:

1. Chemical compounds corresponding to the general formula 5 RC/ \N N/ \CR (RHN & -s[o..R,..-1(oN)1s J Li (Nna)l C C.- L a j L s N N where n is an integer and is at least 1 and 'not employed in the ratio of two mcls of the former to more than 2, and R represents a member of the one mol of the latter. class consisting of hydrogen and monovalent 11. A method as in claim 10 wherein the hydrohydrocarbon and halo-hydrocarbon radicals. 60 halide acceptor is an alkali-metal hydroxide.

2. Chemical compounds as in claim 1 wherein 12. The method of preparing alpha,v beta-bis R represents hydrogen. .6-diamino PY Y J cya oethylene disul- 3. Chemical compounds as in claim 1 wherein flide which comp i s eflecting reaction, in the V n is 1, presence of a hydrohalide acceptor, between 4,6- 4. Chemical compounds corresponding to the 65 diamino 2-mercapto pyrimidine and alpha, betageneral formula dichloropropionitrile in the ratio of two mols of t (L [n-c N sf .CR (mm J5 -SiC.R:--1(CN)]S- -(Nna),

L l L the former to one moi of the latter. where n is an integer and is at least 1, and not GAEI'ANO F. DALELIO. more than 2, and R represents a member of the 7 JAMES W. UNDERWOOD. Y

class consisting of hydrogen and monovaient hydrocarbon and halohydrocarbon radicals.

5. Chemical compounds corresponding to the general formula I where R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals.

6. A bis-(diamino pyrimidyl) cyanomethylene disulfide.

7. Bis- (4,6-diamino pyrimidyl-2) cyanomethylene disulfide.

8. A bis- (diamino pyrimidyl) cyanoethylene dicyanoethylene disulfide.

10. The method of preparing chemical compounds corresponding to the general formula S-[C-R|n-i( I where n is an integer and is at least 1 and not more than 2 and It represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals, said method comprising eflecting reaction, in the presence of a hydrohalide acceptor, between (1) a mercapto pyrimidine corresponding to the general formula l- --s H (RHN u N N/ where R has the meaning above given, and (2) a (ii-halogenated alkyl cyanide corresponding to the general formula Xa- (C-nRh-l) CN where X represents halogen and n and B have the meanings above given, said reactants being CERTIFICATE OF CORRECTION.

Patent No. 23 M569. July 15, 1911.5-

GAETANO F. D ALELIO, ET AL.

of the above numbered patent requiring correction as follows: Page 1, first column, line 1+2, for "cylcopentenyl" read yclopentenyl-; page 5, sec 0nd column, line 70-71,for 'diaminopyrimidyl read -diamino pyrimidyl"; line 72, after "pyrim'idyl" insert abracket; page first colun n, line 70,

in the formula, for "CnR read --C H and that the said Lett Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 51st day of August, A. D. 1915.

Henry Van Arsd ale, Acting Commissioner of Patents. 

